New! View global litigation for patent families

US9427935B2 - Thermoformable three dimensional retroreflective article and method of manufacture - Google Patents

Thermoformable three dimensional retroreflective article and method of manufacture Download PDF

Info

Publication number
US9427935B2
US9427935B2 US12620028 US62002809A US9427935B2 US 9427935 B2 US9427935 B2 US 9427935B2 US 12620028 US12620028 US 12620028 US 62002809 A US62002809 A US 62002809A US 9427935 B2 US9427935 B2 US 9427935B2
Authority
US
Grant status
Grant
Patent type
Prior art keywords
sheet
microbeads
layer
protective
retroreflective
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active, expires
Application number
US12620028
Other versions
US20100124632A1 (en )
Inventor
Michael E. Hannington
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Avery Dennison Corp
Original Assignee
Avery Dennison Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Grant date

Links

Images

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/16Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer formed of particles, e.g. chips, powder, granules
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/14Layered products comprising a layer of synthetic resin next to a particulate layer
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/36Layered products comprising a layer of synthetic resin comprising polyesters
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B3/00Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form ; Layered products having particular features of form
    • B32B3/02Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form ; Layered products having particular features of form characterised by features of form at particular places, e.g. in edge regions
    • B32B3/08Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form ; Layered products having particular features of form characterised by features of form at particular places, e.g. in edge regions characterised by added members at particular parts
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/06Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00Layered products characterised by the relation between layers, i.e. products comprising layers having different physical properties and products characterised by the interconnection of layers
    • B32B7/04Layered products characterised by the relation between layers, i.e. products comprising layers having different physical properties and products characterised by the interconnection of layers characterised by the connection of layers
    • B32B7/12Layered products characterised by the relation between layers, i.e. products comprising layers having different physical properties and products characterised by the interconnection of layers characterised by the connection of layers using an adhesive, i.e. any interposed material having adhesive or bonding properties
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS, OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/12Reflex reflectors
    • G02B5/126Reflex reflectors including curved refracting surface
    • G02B5/128Reflex reflectors including curved refracting surface transparent spheres being embedded in matrix
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00Coating on the layer surface
    • B32B2255/04Coating on the layer surface on a particulate layer
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00Coating on the layer surface
    • B32B2255/20Inorganic coating
    • B32B2255/205Metallic coating
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2264/00Composition of particles which form a particulate layer or are present as additives
    • B32B2264/10Inorganic particles
    • B32B2264/101Glass particles
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2264/00Composition of particles which form a particulate layer or are present as additives
    • B32B2264/10Inorganic particles
    • B32B2264/107Ceramic particles
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/40Properties of the layers or laminate having particular optical properties
    • B32B2307/402Coloured
    • B32B2307/4026Coloured within the layer by addition of a colorant, e.g. pigments, dyes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/40Properties of the layers or laminate having particular optical properties
    • B32B2307/412Transparent
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/40Properties of the layers or laminate having particular optical properties
    • B32B2307/416Reflective
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/40Properties of the layers or laminate having particular optical properties
    • B32B2307/422Luminescent, fluorescent, phosphorescent
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2437/00Clothing
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2590/00Signboards, advertising panels, road signs
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2605/00Vehicles
    • B32B2605/08Cars
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/24Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24355Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
    • Y10T428/24364Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.] with transparent or protective coating

Abstract

A three dimensional retroreflective article having an outer surface with a reflectivity of at least about 200 lux, and method for making such an article from a thermoformable laminate is provided. The laminate includes a base layer of thermoformable plastic sheet material; and a layer of microbeads configured in a high-density arrangement and silvered on their bottom sides to enhance retroreflectivity. The microbeads are adhered to an outer surface of the base layer by a thermoformable cushion coat which may include a phosphorescent pigment to further enhance reflectivity. A protective sheet of transparent thermoformable sheet material overlies and may be in contact with the layer of microbeads. The laminate is heated and thermoformed into a self supporting three dimensional article having a pre-selected shape and an encapsulated bead retroreflective surface having a reflectivity of at least about 200 lux. The thermoforming step imparts sufficient non-planarity in the resulting retroreflective surface so that retroreflective dead spots created by contact between the microbeads and the protective sheet of transparent sheet material are effectively optically cancelled by overlapping zones of retroreflectivity generated by the microbeads.

Description

CROSS-REFERENCE TO RELATED APPLICATION

The present application claims the benefit of U.S. Provisional Patent Application No. 61/115,567 filed Nov. 18, 2008, which is incorporated herein by reference in its entirety.

FIELD OF THE INVENTION

This invention generally relates to articles made from thermoformable retroreflective sheet materials, and is specifically concerned with three dimensional retroreflective articles formed from thermoformable materials that include an outer surface with a reflectivity of at least about 200, and method for making such an article from a thermoformable laminate.

BACKGROUND OF THE INVENTION

Retroreflective articles employing an outer layer of microbeads are known in the prior art. In one method of manufacture, a bead-containing coating is applied over the outer surface of the article (which may be, for example, protective helmet). The coating is allowed to dry, and is then etched to expose the microbeads. Later, a transparent sheet of vinyl chloride or other polymeric material is molded into the same shape as the article, and mounted over the outside surface, advantageously encapsulating them while leaving a small air space between the transparent material and the tops of the microbeads. Such encapsulation both protects the beads and prevents direct contact between the beads and ambient moisture, which could interfere with their retroreflective properties.

In another method of manufacture, a flexible, microbead-containing sheet material is applied over the outer surface of the article. Such sheet materials are known which have a sufficient amount of stretch to allow them to be evenly adhered over the surfaces of embossed license plates, road cones and road markers. In still another method, a microbead containing, non-woven fabric is used to make retroreflective vests and other garments for highway workers working at night.

Unfortunately, none of the known manufacturing techniques is believed to be capable of easily and quickly producing a rigid three-dimensional article having an encapsulated bead outer surface capable of high intensity retroreflection (defined in this application as a reflectivity of between about 200 to about 300 lux) without further manufacturing or assembly steps. The application and processing of a bead-containing coating over the surface of such an article is relatively cumbersome and time consuming Moreover, it is difficult to obtain the kind of high-density arrangement of the microbeads necessary to achieve high retroreflectivities of about 200 lux or more due to the irregular heights and distribution of the beads in the bonding material. Finally, such a method requires the separate fabrication and application of a protective transparent sheet material over the bead layer to encapsulate the beads.

While the application of a flexible, bead-containing retroreflective sheet material over the surface of the article may be practical for articles having simple shapes (such as license plates, road cones and other generally planar items), and does allow for a uniform and high density arrangement of microbeads, it is clearly more difficult to uniformly apply to tightly rounded and complex shapes, such as protective helmets with reinforcing ridges, protective padding or guards (e.g. knee pads, shine guards) or highly contoured shapes, such as automotive bumpers, body panels, grills and mirror housings. Of course, such a method might be modified such that only strips of retroreflective were applied to the article. However, such a modification would compromise the visibility and total reflectivity of the surface. Additionally, while many such flexible retroreflective sheet materials include a protective coating of transparent material over the bead layer, they do not include an encapsulating protective transparent sheet material that provides an air space over the bead layer. The use of such an “enclosed bead structure” in such sheet materials undesirably limits the retroreflectivity of the article to about 180 lux or less.

Clearly, there is a need for method for producing a self-supporting three dimensional article having a high-intensity retroreflective surface which is easier and less time consuming than the aforementioned prior art methods. Ideally, such a method would be easily applicable to virtually any shape, and would allow the microbeads to be arranged over the entire outer surface of the article in a high-density configuration to maximize retroreflectivity. Finally, such a method would provide a transparent sheet material over the layer of microbeads to provide the advantages of encapsulation without the need for additional fabricating steps.

SUMMARY OF THE INVENTION

Generally speaking, the invention is both a three dimensional (substantially non-planar) retroreflective article, a laminate and method for making such an article having an outer surface with a reflectivity of at least about 200 lux that overcomes the aforementioned shortcomings associated with the prior art. A principle aspect of the invention stems from the applicant's observation that the thermoforming of an encapsulated microbead retroreflective sheet material, under certain conditions, can produce a three dimensional article of virtually any shape with a high reflectivity of about 200-300 lux. Previous to the applicant's invention, it was thought that the necessary softening of any transparent encapsulating layer overlying a thermoformable microbead laminate would cause the encapsulating layer to fuse over the tops of the microbeads, thereby fatally destroying the necessary airspace between the microbeads and the encapsulating layer and creating reflection-degrading “dead spots” over the tops of the microbeads which would make it impossible to achieve high-intensity retroreflectivity. Contrary to conventional wisdom, applicant observed through experimentation that the “dead spot” phenomenon could be made far smaller than anticipated by the use of variable-diameter microbeads (mircrobeads which are non-uniformly sized) and the use of selected types of polymers for the encapsulating layer which “pull-back” as a result of cooling after thermoforming, thereby recreating the necessary air space. The problems associated with dead spots are apparently further concealed or largely cancelled out by the overlapping zones of retroreflectivity caused by the contours of most three dimensional articles.

Accordingly, the retroreflective three dimensional article of the invention comprises a laminate formed from a base or first layer of thermoformable plastic sheet material, the first layer having first and second sides; a layer of retroreflective microbeads adhered to an outer surface or first side of said base material by a thermoformable cushion coat, and a protective sheet or second layer of transparent thermoformable sheet material overlying the layer of microbeads, where there is some variation in the diameter of the microbeads. The laminate is thermoformed into a self supporting three dimensional article, which is generally non-planar, having a pre-selected shape and an encapsulated bead retroreflective surface having a reflectivity of at least about 200 lux. The protective sheet may be in contact with some of the microbeads, and may be colored. The microbeads are configured in a high-density arrangement and are silvered on their bottom sides to provide high-intensity retroreflection. The cushion coat may include a phosphorescent pigment to further enhance reflectivity, and is preferably a layer of binder containing a polyvinyl copolymer, a thermoplastic polyurethane, and an aminoplast resin. The transparent layer preferably has a thickness of between about 4-8 times an average diameter of the microbeads, and the base layer preferably has a thickness of between about 4 to 12 times an average diameter of the microbeads. Such a ratio facilitates the thermoforming method of the invention while still providing the amount of rigidity to the completed article necessary for it to preserve its shape. Both the protective transparent layer and the base layer may be formed from a thermoformable plastic material such as PETG (glycol-modified polyethylene terephthalate). The use of PETG as the protective transparent layer advantageously results in some degree of “pull back” from the microbeads upon cooling after thermoforming The use of variable diameter microbeads limits fusing contact between the protective transparent layer and only the largest diameter microbeads. The surface of the three dimensional article preferably is sufficiently non-planar so that retroreflective dead spots created by limited amount of contact between the microbeads and the protective sheet of transparent sheet material are effectively optically cancelled by overlapping zones of retroreflectivity generated by the microbeads.

The method of the invention generally comprise the steps of adhering, via aforementioned cushion coat, a plurality of retroreflective, semi-silvered microbeads in a high-density arrangement onto the base layer of thermoformable plastic sheet material; overlying the protective sheet of transparent, thermoformable sheet material in contact with the retroreflective microbeads adhered to the base layer to form a generally flat combination layer; applying sufficient heat to the combination layer to render it thermoformable, and thermoforming the heated combination layer into a three dimensional article having a pre-selected shape and an encapsulated bead retroreflective surface having a reflectivity of at least about 200 lux. Preferably, the thermoforming step imparts sufficient non-planarity in the resulting retroreflective surface so that retroreflective dead spots created by contact between the microbeads and the protective sheet of transparent sheet material are effectively optically cancelled by overlapping zones of retroreflectivity generated by the microbeads.

BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS

FIG. 1 illustrates the first step in the method of assembling the thermoformable laminate of the invention, wherein microbeads are adhered in a dense arrangement and randomly distributed over a donor sheet consisting of layer of adhesive overlying a support layer of polyethylene terephthalate;

FIG. 2 illustrates the step of metallizing the bottom halves of the microbeads on the donor sheet;

FIG. 3 illustrates the step of applying an adhesive cushion coat over a removable substrate;

FIG. 4 illustrates the step of adhering a thermoformable support sheet over the exposed surface of the cushion coat and peeling off the removable substrate;

FIG. 5 illustrates the step of pressing the thermoformable support sheet and the exposed surface of the adhesive cushion coat onto the layer of metallized beads on the top surface of the donor sheet;

FIG. 6 illustrates how the adhesive cushion coat removes the layer of metallized beads from the donor sheet;

FIG. 7 illustrates the laminate resulting from the step illustrated in FIG. 6;

FIG. 8 illustrates the final step of assembling the thermoformable laminate of the invention, wherein a protective sheet of thermoformable, transparent sheet material is positioned over the microbeads adhered over the substrate of thermoformable plastic material;

FIG. 9 is an enlargement of the area circled in phantom in FIG. 7 and illustrates how the natural variation in the diameter of the microbeads causes only some of the microbeads to tangentially contact the underside of the transparent protective sheet material prior to thermoforming;

FIG. 10 illustrates how the softening of the protective, transparent sheet material during thermoforming of the laminate causes the sheet to sag and fusingly contact the top ends of the microbeads;

FIG. 11 illustrates how the transparent, protective sheet material shown in FIG. 10 “pulls back” out of contact with many of the microbeads after cooling, thereby leaving most of the microbeads with an air space between the transparent protective sheet and the tops of the microbeads, and

FIG. 12 illustrates how a three dimensional helmet shell thermoformed from the laminate illustrated in FIG. 11 is rapidly assembled over a conventional construction safety helmet to render it brightly retroreflective.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

FIGS. 1 and 2 illustrate the first steps in fabricating the thermoformable laminate used in the method of making the high intensity retroreflective article of the invention. In these first steps, a bead donor sheet 1 is prepared by adhering a 1 mil thick sheet 3 of low density polyethylene over a 3 mil thick layer of a substrate 5, which in this example is a sheet of polyethylene terephthalate. Heat is next applied to the resulting bead donor sheet 1 via a heat source (not shown) in order to soften the 1 mil thick sheet 3 of low density polyethylene. The substrate 5, having a higher melting point, is able to support the softened sheet 3 throughout this step. Glass or ceramic microbeads 6 are next applied over the softened sheet 3. Preferably, the microbeads 6 have an average diameter of between about 40 and 90 microns, with a variation of ±15%. For example, if microbeads having an average diameter of 50 microns are selected, the range of diameters would vary between 42.5 microns to 57.5 microns. As will be discussed in more detail hereinafter, such a variation in diameter advantageously creates air spaces between most of the microbeads and the transparent protective sheet that ultimately forms the top layer of the resulting thermoformable laminate. The beads 6 are applied over the heat-softened, 1 mil thick sheet 3 of low density polyethylene in a high-density arrangement where the beads 6, on average, are practically touching one another.

As shown in FIGS. 1 and 2, the microbeads 6 sink into the heat softened sheet 3 until their bottom halves are at least partially embedded into the low density polyethylene forming the sheet 3. The heat source is removed in order to allow the donor sheet 1 to cool and the 1 mil thick sheet 3 of low density polyethylene to harden, which in turn weakly adheres the microbeads 7 to the donor sheet 1. Next, as schematically indicated in FIG. 2, the exposed hemispheres of the beads 6 are metallized by the application of a thin layer 9 on the order of 300 nanometers of vapor-deposited aluminum. This step results in a bead donor sheet 1 having a high density layer 8 of semi-metallized microbeads 7 weakly adhered to the sheet 3 of low density polyethylene.

Separately from the fabrication of the bead donor sheet, an adhesive cushion coat 11 is applied to a thermoformable support sheet 15, as illustrated in FIGS. 3 and 4. This is accomplished by first applying a cushion coat 11 over a 2 mil thick sheet 13 of polyethylene terephthalate, as schematically illustrated in FIG. 3. Preferably, the cushion coat 11 is formed from a layer of white pigmented binder containing a polyvinyl copolymer, a thermoplastic polyurethane, and an aminoplast resin as disclosed in Levenstein U.S. Pat. No. 6,586,067, and assigned to the Avery Dennison Corporation the common assignee of the instant application. The thickness of the cushion coat 11 is approximately ⅔ the average diameter of the beads, or about 2 mils. To enhance the reflectivity of the laminate that ultimately results form these steps, the cushion coat may include a phosphorescent pigment. The exposed face of the cushion coat 11 is next heat laminated to a thermoformable support sheet 15, as schematically indicated in FIG. 4. Preferably, support sheet 15 is a 20-30 mil thick sheet of glycol-modified polyethylene terephthalate, although other thermoformable plastic materials may also be used. Finally, the 2 mil thick sheet 13 of polyethylene terephthalate is peeled off of the cushion coat 11, as is also indicated in FIG. 4. This is easily done as the cushion coat 11 is adhered more strongly to the support sheet 15 of glycol-modified polyethylene terephthalate as a result of the heat lamination than to the 2 mil thick sheet 13 of polyethylene terephthalate. This step results in a sub-laminate 16 a consisting of the support sheet 15 and cushion coat 11.

FIGS. 5 and 6 illustrate how the bead donor sheet 1 of FIG. 2 and the sub-laminate 16 a of FIG. 4 are brought together to form a beaded sub-laminate 16 b formed from the layer 8 of semi-metallized microbeads 7, the cushion coat 11, and the support sheet 15. In these steps of the method, the exposed side of the cushion coat 11 is positioned over the layer 8 of semi-metallized microbeads 7 overlying the donor sheet 1 and is pressed into contact so that the cushion coat 11 adheres to the metallized hemispheres of the beads 7, as indicated in FIG. 5. Next, the support sheet 15 and cushion coat 11 is lifted off of the face of the donor sheet 1, as is indicated in FIG. 6. As the cushion coat strongly adheres to the microbeads 7, and the solidified sheet 3 of low density polyethylene of the donor sheet adheres only weakly to the microbeads 7, the layer 8 of semi-metallized microbeads is lifted off of the donor sheet, forming a beaded sub-laminate 16 b.

FIGS. 7 and 8 illustrate the final steps in forming the laminate used in fabricating the high-intensity retroreflective articles of the invention. The beaded sub-laminate 16 b or combination layer formed in the step illustrated in FIG. 6 is removed from the donor sheet 1 and righted into the position illustrated in FIG. 7. A thermoformable, transparent sheet material 17 is positioned over the sub-laminate 16 b to form the thermoformable laminate 18 used to fabricate the three dimensional articles of the invention. While the sheet material 17 is preferably transparent, it may be colored or tinted as desired to give the final article formed from the laminate 18 a desired color or appearance. Alternatively, the sheet material 17 may possess a color-neutral transparency and a desired coloring of the final article may be achieved by the inclusion of a coloring pigment (either phosphorescent or otherwise) in the cushion coat 11. The transparent sheet material 17 may be placed over the beaded sub-laminate 16 b either before, after, or at the time of the thermoforming of the beaded sub-laminate 16 b into a three dimensional article. In the preferred embodiment, transparent sheet material 17 is a 20-30 mil thick sheet of glycol-modified polyethylene terephthalate, as such a plastic would have substantially the same thermoforming characteristics as the support sheet 15 (which is also formed from glycol-modified polyethylene terephthalate) and would have sufficient thickness to both protect the bead layer 8 and to contribute to the desired, self-supporting rigidity of the final thermoformed article.

FIGS. 9, 10 and 11 illustrate how the laminate 18 of the invention advantageously maintains its high intensity retroreflective optical characteristics through the process of thermoforming the laminate into a three dimensional article. Specifically, FIG. 9 is an enlargement of the area circled in phantom shown by reference numeral 9 in FIG. 8, and illustrates in particular the interface between the tops of the bead 7 and the lower surface 19 of the transparent protective sheet 17. Due to the natural variation in the diameter of the beads 7, as well as variations in the depth “D” that these beads extend into the cushion coat 11, there are variations in the relative height “H” in the beads 7. As a consequence, the only contact between the transparent protective sheet 17 and the beads 7 is tangential point contact 20 between the lower surface 19 and the tops of only the highest beads 7. Such contact advantageously leaves air spaces 21 a, 21 b and 21 c of varying widths between the tops of the other beads and the lower surface 19 of the transparent protective sheet 17 which in turn allows the microbeads 7 to operate at maximum retroreflectivity with only a small number of narrow-angle “dead spots” caused by the infrequent tangential point contact 20 between the microbeads 7 and the lower surface 19 of the transparent protective sheet 17.

FIG. 10 illustrates how the interface between the lower surface 19 and the tops of the microbeads 7 changes when the transparent protective sheet 17 is heat-softened incident to the thermoforming of the laminate 18 into a three dimensional article. Preferably, such heat softening of the sheet 17 occurs simultaneously with the heat softening of the sub-laminate 16 b in order to minimize the amount of time, steps and power necessary to thermoform a three dimensional article of the invention. However, if desired, the transparent protective sheet 17 may be separately thermoformed over an article thermoformed from the sub-laminate 16 b. FIG. 10 is applicable to both variations in the method of the invention, and illustrates how the softening and drawing down of the transparent protective sheet 17 over the tops of the microbeads 7 broadens the interface between the lower surface 19 and the microbeads to areas 23 a, 23 b and 23 c of fusing contact of varying sizes, such areas being largest (23 a) between the highest microbeads and smaller (23 b and 23 c) with lower microbeads, but nonexistent between the lowest microbeads 7 and the lower surface 19 (note air space 21 b). If left uncorrected, the substantial number amount and areas of fusing contact between the microbeads 7 and the lower surface 19 of the transparent protective sheet 17 could seriously impair the retroreflective ability of the beads 7 due to the number and broad angularity of the optical “dead spots” resulting from such interfaces.

FIG. 11 illustrates how the specific thicknesses and composition of the transparent protective sheet 17 eliminates much of the fusing contact between the microbeads 7 and the lower surface 19 when the transparent protective sheet 17 is allowed to cool after a thermoforming operation. The applicant has found that the thermal contraction of a transparent protective sheet of the aforementioned composition and thickness range results in “pull back” of the lower surface 19 from the tops of the microbeads that either eliminates or at least substantially reduces the resulting final amount of contact between the lower surface 19 and the microbeads 7 such that an air space 21 a, 21 b is restored between the surface 19 and about half or more of the microbeads.

FIG. 12 illustrates a practical application of a high retroreflectivity, three dimensional article in the form of an outer hard hat shell 27. In this example of the invention, shell 27 is thermoformed from the laminate 18 in the same shape as the outer surface of a hard hat 31. The shell 27 may include flanges (not shown) around its lower edge 29 that “snap fit” around the lower edge 32 of the hard hat to secure it firmly in place. The hard hat 31 is in turn formed from a layer 33 of fiberglass composite to give it the strength required to protect construction workers from falling objects in a construction site. Such shells have actually been fabricated by the applicant in accordance with the method and laminate described herein, and have a measured reflectivity of about 300 lux due to the large number of microbeads 7 that do not come into fusing contact with the lower surface of the transparent protective sheet 17 due to the variations in bead height coupled with the previously described “pull back” phenomenon that occurs upon the cooling of a transparent protective sheet 17 selected in conformance with the invention. Additionally, the applicant has noted that to the extent that fusing contact between the microbeads 7 and the lower surface 19 exists after cooling of the sheet 17, the effect of the resulting optical “dead spots” is neutralized by the overlapping of the zones of retroreflectivity of the microbeads 7 caused by the curvature and contours which are naturally part of any three dimensional article.

Different modifications, additions, and variations of this invention may become evident to the persons in the art. For example, the transparent protective sheet 17 could be separately thermoformed from the sub-laminate 16 b and snap-fitted over the layer 8 of microbeads of the article.

It will thus be seen according to the present invention a highly advantageous thermoformable laminate for use in creating generally non-planar, three dimensional objects has been provided. While the invention has been described in connection with what is presently considered to be the most practical and preferred embodiment, it will be apparent to those of ordinary skill in the art that the invention is not to be limited to the disclosed embodiment, and that many modifications and equivalent arrangements may be made thereof within the scope of the invention, which scope is to be accorded the broadest interpretation of the appended claims so as to encompass all equivalent structures and products.

The inventor hereby states his intent to rely on the Doctrine of Equivalents to determine and assess the reasonably fair scope of their invention as it pertains to any apparatus, system, method or article not materially departing from but outside the literal scope of the invention as set out in the following claims.

Claims (31)

What is claimed is:
1. A three dimensional article having a high intensity retroreflective outer surface, comprising:
a base layer of thermoformable plastic sheet material;
a layer of retroreflective microbeads having a variation in diameter adhered to an outer surface of said base layer, and
a protective sheet of transparent thermoformable sheet material overlying said layer of microbeads, wherein said protective sheet engages a top surface of some of the microbeads to form airspaces and create infrequent tangential point contact between at least a portion of said protective sheet and said some of the microbeads,
wherein said base layer, layer of microbeads, and protective transparent sheet are formed into a self supporting three dimensional article having a pre-selected shape and an encapsulated bead retroreflective surface having a reflectivity of at least about 200 lux,
wherein the protective sheet comprises glycol-modified polyethylene terephthalate (PETG); and
wherein the protective sheet has a thickness of 20 mils to 30 mils.
2. The three dimensional article of claim 1, wherein said protective sheet fusingly engages a top surface of some of the microbeads.
3. The three dimensional article of claim 1, wherein the retroreflective microbeads have an average diameter of between about 2 and 4 mils are adhered to said base layer of thermoformable plastic sheet material by a cushion coat.
4. The three dimensional article of claim 3, wherein the cushion coat comprises a polyvinyl copolymer, a thermoplastic polyurethane, and an aminoplast resin.
5. The three dimensional article of claim 1, wherein the thickness of the base layer is between about 4 to 12 times an average diameter of the microbeads.
6. The three dimensional article of claim 1, wherein the thickness of the protective sheet is between about 2 to 10 times an average diameter of the microbeads.
7. The three dimensional article of claim 1, wherein the base layer is formed from glycol-modified polyethylene terephthalate (PETG).
8. The three dimensional article of claim 1, wherein the microbeads have a silvered side that is adheringly engaged to said base layer by means of a thermoformable cushion coat.
9. The three dimensional article of claim 8, wherein the cushion coat comprises a polyvinyl copolymer, a thermoplastic polyurethane, and an aminoplast resin.
10. The three dimensional article of claim 1 having airspaces between the protective sheet and at least half of the microbeads.
11. The three dimensional article of claim 1, wherein the thickness of the protective sheet is between about 4 to 8 times an average diameter of the microbeads.
12. A thermoformable, high intensity retroreflective laminate, comprising:
a base sheet of thermoformable plastic;
a layer of retroreflective microbeads having a variation in diameter adhered over one surface of the base sheet;
a protective sheet of clear thermoformable plastic laminated over said layer of retroreflective beads, wherein said protective sheet engages a top surface of some of the microbeads to form airspaces and create infrequent tangential point contact between at least a portion of said protective sheet and said some of the microbeads,
wherein said laminate is thermoformable into a contoured, three dimensional article having an encapsulated bead surface with a reflectivity of at least 200 lux,
wherein the protective sheet comprises glycol-modified polyethylene terephthalate (PETG); and
wherein the protective sheet has a thickness of 20 mils to 30 mils.
13. The high intensity retroreflective laminate of claim 12, wherein said base layer of sheet material has a thickness of between about 4 and 12 times an average diameter of the microbeads.
14. The high intensity retroreflective laminate of claim 12, wherein the thickness of the protective sheet is between about 2 to 10 times an average diameter of the microbeads.
15. The high intensity retroreflective laminate of claim 12, wherein the retroreflective microbeads have an average diameter of between about 2 and 4 mils and are adhered to said layer of thermoformable plastic sheet material by a cushion coat.
16. The high intensity retroreflective laminate of claim 15, wherein the cushion coat comprises a polyvinyl copolymer, a thermoplastic polyurethane, and an aminoplast resin.
17. The high intensity retroreflective laminate of claim 12, wherein the base layer is formed from PETG.
18. The high intensity retroreflective laminate of claim 12, wherein the microbeads are semi-silvered, having a silvered side that is adheringly engaged to said base layer by means of a thermoformable cushion coat.
19. The high intensity retroreflective laminate of claim 18, wherein the cushion coat comprises a polyvinyl copolymer, a thermoplastic polyurethane, and an aminoplast resin.
20. The laminate of claim 12 having airspaces between the protective sheet and at least half of the microbeads.
21. The high intensity retroreflective laminate of claim 12, wherein the thickness of the protective sheet is between about 4 to 8 times an average diameter of the microbeads.
22. A thermoformable, high intensity retroreflective laminate, comprising:
a base sheet of thermoformable plastic;
a layer of retroreflective microbeads adhered over one surface of the base sheet by way of a thermoformable cushion coat, each of said beads having a semisilvered side engaging the cushion coat;
a protective sheet of clear thermoformable plastic laminated over and in contact with said layer of retroreflective beads, wherein said protective sheet engages a top surface of some of the microbeads to form airspaces and create infrequent tangential point contact between at least a portion of said protective sheet and said some of the microbeads,
wherein said laminate is capable of being formed into a contoured, three dimensional article having an encapsulated bead surface with a reflectivity of at least 200 lux, said base layer of sheet material has a thickness of between about 4 and 12 times an average diameter of the microbeads, and the thickness of the protective sheet is between about 2 to 10 times an average diameter of the microbeads;
wherein the protective sheet comprises glycol-modified polyethylene terephthalate (PETG); and
wherein the protective sheet has a thickness of 20 mils to 30 mils.
23. The thermoformable, high intensity retroreflective laminate defined in claim 22, wherein said cushion coat includes a phosphorescent pigment to enhance the reflectivity of said surface.
24. The laminate of claim 22 having airspaces between the protective sheet and at least half of the microbeads.
25. The high intensity retroreflective laminate of claim 22, wherein the thickness of the protective sheet is between about 4 to 8 times the average diameter of the microbeads.
26. The high intensity retroreflective laminate of claim 23, wherein the cushion coat comprises a polyvinyl copolymer, a thermoplastic polyurethane, and an aminoplast resin.
27. The high intensity retroreflective laminate of claim 22, wherein the cushion coat comprises a polyvinyl copolymer, a thermoplastic polyurethane, and an aminoplast resin.
28. A thermoformable retroreflective laminate for substantially non-planar articles, comprising;
a first thermoformable layer having first and second sides;
a plurality of non-uniformly sized microbeads disposed randomly on said first side of said first layer, said microbeads having a reflectivity of at least about 200 lux and being disposed substantially over said first side;
a second thermoformable layer having first and second sides, said second thermoformable layer contacting at least some of said microbeads;
an airspace formed between at least a part of said second thermoformable layer and said microbeads,
wherein said first and second layer with said microbeads disposed therebetween is formed in-situ creating a substantially non-planar article having at least a partially retroreflective surface,
wherein said second thermoformable layer comprises glycol-modified polyethylene terephthalate (PETG); and
wherein the protective sheet has a thickness of 20 mils to 30 mils.
29. A thermoformable retroreflective laminate as recited in claim 28, wherein said airspace varies in width between said second thermoformable layer and said microbeads.
30. The thermoformable retroreflective laminate of claim 28, wherein the thickness of the second thermoformable layer is between about 4 to 8 times an average diameter of the microbeads.
31. A thermoformable, high intensity retroreflective laminate, comprising:
a base sheet of thermoformable plastic;
a layer of retroreflective microbeads adhered over one surface of the base sheet by way of a thermoformable cushion coat, each of said beads having a semisilvered side engaging the cushion coat;
a protective sheet of clear thermoformable plastic laminated over and in contact with said layer of retroreflective beads, wherein said protective sheet engages a top surface of some of the microbeads to form airspaces and create infrequent tangential point contact between at least a portion of said protective sheet and said some of the microbeads,
wherein said laminate is capable of being formed into a contoured, three dimensional article having an encapsulated bead surface with a reflectivity of at least 200 lux, said base layer of sheet material has a thickness of between about 4 and 12 times an average diameter of the microbeads, and the thickness of the protective sheet is between about 4 to 8 times an average diameter of the microbeads,
wherein the protective sheet comprises glycol-modified polyethylene terephthalate (PETG),
wherein the cushion coat comprises a polyvinyl copolymer, a thermoplastic polyurethane, and an aminoplast resin; and
wherein the protective sheet has a thickness of 20 mils to 30 mils.
US12620028 2008-11-18 2009-11-17 Thermoformable three dimensional retroreflective article and method of manufacture Active 2031-04-17 US9427935B2 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US11556708 true 2008-11-18 2008-11-18
US12620028 US9427935B2 (en) 2008-11-18 2009-11-17 Thermoformable three dimensional retroreflective article and method of manufacture

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US12620028 US9427935B2 (en) 2008-11-18 2009-11-17 Thermoformable three dimensional retroreflective article and method of manufacture
US15182930 US9821531B2 (en) 2008-11-18 2016-06-15 Thermoformable three dimensional retroreflective article and method of manufacture

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US15182930 Division US9821531B2 (en) 2008-11-18 2016-06-15 Thermoformable three dimensional retroreflective article and method of manufacture

Publications (2)

Publication Number Publication Date
US20100124632A1 true US20100124632A1 (en) 2010-05-20
US9427935B2 true US9427935B2 (en) 2016-08-30

Family

ID=41622418

Family Applications (2)

Application Number Title Priority Date Filing Date
US12620028 Active 2031-04-17 US9427935B2 (en) 2008-11-18 2009-11-17 Thermoformable three dimensional retroreflective article and method of manufacture
US15182930 Active US9821531B2 (en) 2008-11-18 2016-06-15 Thermoformable three dimensional retroreflective article and method of manufacture

Family Applications After (1)

Application Number Title Priority Date Filing Date
US15182930 Active US9821531B2 (en) 2008-11-18 2016-06-15 Thermoformable three dimensional retroreflective article and method of manufacture

Country Status (6)

Country Link
US (2) US9427935B2 (en)
EP (2) EP2359168B1 (en)
KR (1) KR20110087294A (en)
CN (1) CN102282483B (en)
ES (2) ES2559938T3 (en)
WO (1) WO2010059600A1 (en)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8727565B2 (en) 2009-09-14 2014-05-20 James L. Ecker LED lighting devices having improved light diffusion and thermal performance
US20110062868A1 (en) * 2009-09-14 2011-03-17 Domagala Thomas W High luminous output LED lighting devices
KR101206376B1 (en) * 2012-07-20 2012-11-29 (주)에이치제이 Method for fabricating retroreflective sheet
US9155346B2 (en) * 2012-10-18 2015-10-13 Cing Wai Kung Mau Company Process for reflective products
CN104777533A (en) * 2015-03-18 2015-07-15 深圳桃园大新智能穿戴技术有限公司 Fully-reflective material and preparation method thereof as well as fully-reflective fabric
US9864112B1 (en) 2016-11-16 2018-01-09 3M Innovative Properties Company Conformable retroreflective graphic film

Citations (31)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2354048A (en) 1940-08-03 1944-07-18 Minnesota Mining & Mfg Flexible lenticular optical sheet
US2354018A (en) 1940-08-03 1944-07-18 Minnesota Mining & Mfg Light reflector sheet
US2354049A (en) 1944-01-19 1944-07-18 Minnesota Mining & Mfg Backless reflex light reflector
US2403752A (en) 1940-02-13 1946-07-09 Brown & Bigelow Flexible reflex reflecting film
US2948191A (en) 1956-06-06 1960-08-09 Cataphote Corp Retroreflecting surface
US3190178A (en) 1961-06-29 1965-06-22 Minnesota Mining & Mfg Reflex-reflecting sheeting
US3885246A (en) 1973-11-05 1975-05-27 Minnesota Mining & Mfg Retroreflective protective helmet
US3971692A (en) 1974-07-02 1976-07-27 Anderson Nigel I Retro-reflective materials
US4102562A (en) 1976-06-14 1978-07-25 Minnesota Mining And Manufacturing Company Retroreflective transfer sheet material
US4272564A (en) 1979-06-27 1981-06-09 C. M. Offray & Son, Inc. Flexible reflex-reflective article having undulant surface and method of making the same
US4496618A (en) 1982-09-30 1985-01-29 Pernicano Vincent S Heat transfer sheeting having release agent coat
US4605461A (en) 1983-12-15 1986-08-12 Ide Idustries Limited Method of transferring a retroreflective pattern onto a fabric
US4678695A (en) 1985-12-23 1987-07-07 Minnesota Mining And Manufacturing Company Encapsulated flattop retroreflective sheeting and method for producing the same
US5064272A (en) 1985-11-18 1991-11-12 Minnesota Mining And Manufacturing Company Encapsulated-lens retroreflective sheeting and method of making
US5069964A (en) 1989-05-23 1991-12-03 Minnesota Mining And Manufacturing Company Flexible, substrate-insular retroreflective sheeting
EP0602599A1 (en) 1992-12-16 1994-06-22 Minnesota Mining And Manufacturing Company Supported encapsulated-lens retroreflective sheeting
US5415911A (en) * 1992-01-16 1995-05-16 Stimsonite Corporation Photoluminescent retroreflective sheeting
EP0693697A2 (en) 1994-07-22 1996-01-24 Nippon Carbide Kogyo Kabushiki Kaisha A method for producing retroreflective sheeting
WO1996035970A1 (en) 1995-05-11 1996-11-14 Minnesota Mining And Manufacturing Company Encapsulated lens retroreflective sheeting having thermoplastic polyurethane bonding layer
US5601915A (en) 1994-03-18 1997-02-11 Nippon Carbide Kogyo Kabushiki Kaisha Retroreflective sheeting
WO1997010378A1 (en) 1995-09-15 1997-03-20 Minnesota Mining And Manufacturing Company Retroreflective transfer sheet and applique
US5812316A (en) 1992-10-23 1998-09-22 Nippon Carbide Kogyo Kabushiki Kaisha Method for making retroreflective sheeting
US5835271A (en) 1995-06-29 1998-11-10 Minnesota Mining And Manufacturing Company Encased retroreflective elements and method for making
US5959775A (en) 1997-12-23 1999-09-28 3M Innovative Properties Company Urethane/acrylate bead bond for retroreflective articles
US6156436A (en) 1997-04-04 2000-12-05 3M Innovative Properties Company Use of a crystalline bead bond layer in a retroreflective article
US20030006005A1 (en) * 1998-05-29 2003-01-09 3M Innovative Properties Company Prefabricated retroreflective sign
US6586067B2 (en) 2001-04-02 2003-07-01 Avery Dennison Corporation Encapsulated lens retroreflective sheeting
US20030151815A1 (en) 1998-10-30 2003-08-14 Michael Hannington Retroreflective sheeting containing a validation image and methods of making the same
US6677030B2 (en) 1996-10-23 2004-01-13 3M Innovative Properties Company Retroreflective articles having tackified acrylic adhesives for adhesion to curved low surface energy substrates
US6677028B1 (en) 1999-09-10 2004-01-13 3M Innovative Properties Company Retroreflective articles having multilayer films and methods of manufacturing same
US20060238871A1 (en) 2005-04-21 2006-10-26 Lee In-Hwan Method of producing a retro-reflective heat transfer film with a transparent protective sheet for whole surface

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2014254C (en) * 1989-05-23 2001-07-24 Howard R. Tolliver Flexible, substrate-insular retroreflective sheeting
US5882771A (en) * 1996-04-10 1999-03-16 Minnesota Mining And Manufacturing Company Conformable embossable retroreflective sheeting
WO2006085690A1 (en) * 2005-02-10 2006-08-17 Nippon Carbide Kogyo Kabushiki Kaisha Retroreflection sheet
US8147075B2 (en) * 2005-04-11 2012-04-03 Nippon Carbide Kogyo Kabushiki Kaisha Printed image-set retroreflective sheeting

Patent Citations (35)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2403752A (en) 1940-02-13 1946-07-09 Brown & Bigelow Flexible reflex reflecting film
US2354018A (en) 1940-08-03 1944-07-18 Minnesota Mining & Mfg Light reflector sheet
US2354048A (en) 1940-08-03 1944-07-18 Minnesota Mining & Mfg Flexible lenticular optical sheet
US2354049A (en) 1944-01-19 1944-07-18 Minnesota Mining & Mfg Backless reflex light reflector
US2948191A (en) 1956-06-06 1960-08-09 Cataphote Corp Retroreflecting surface
US3190178A (en) 1961-06-29 1965-06-22 Minnesota Mining & Mfg Reflex-reflecting sheeting
USRE29742E (en) 1973-11-05 1978-08-29 Minnesota Mining And Manufacturing Company Retroreflective protective helmet
US3885246A (en) 1973-11-05 1975-05-27 Minnesota Mining & Mfg Retroreflective protective helmet
US3971692A (en) 1974-07-02 1976-07-27 Anderson Nigel I Retro-reflective materials
US4102562A (en) 1976-06-14 1978-07-25 Minnesota Mining And Manufacturing Company Retroreflective transfer sheet material
US4272564A (en) 1979-06-27 1981-06-09 C. M. Offray & Son, Inc. Flexible reflex-reflective article having undulant surface and method of making the same
US4496618A (en) 1982-09-30 1985-01-29 Pernicano Vincent S Heat transfer sheeting having release agent coat
US4605461A (en) 1983-12-15 1986-08-12 Ide Idustries Limited Method of transferring a retroreflective pattern onto a fabric
US5064272A (en) 1985-11-18 1991-11-12 Minnesota Mining And Manufacturing Company Encapsulated-lens retroreflective sheeting and method of making
US4678695A (en) 1985-12-23 1987-07-07 Minnesota Mining And Manufacturing Company Encapsulated flattop retroreflective sheeting and method for producing the same
US5069964A (en) 1989-05-23 1991-12-03 Minnesota Mining And Manufacturing Company Flexible, substrate-insular retroreflective sheeting
US5415911A (en) * 1992-01-16 1995-05-16 Stimsonite Corporation Photoluminescent retroreflective sheeting
US5812316A (en) 1992-10-23 1998-09-22 Nippon Carbide Kogyo Kabushiki Kaisha Method for making retroreflective sheeting
EP0602599B1 (en) 1992-12-16 1998-10-21 Minnesota Mining And Manufacturing Company Supported encapsulated-lens retroreflective sheeting
EP0602599A1 (en) 1992-12-16 1994-06-22 Minnesota Mining And Manufacturing Company Supported encapsulated-lens retroreflective sheeting
US5601915A (en) 1994-03-18 1997-02-11 Nippon Carbide Kogyo Kabushiki Kaisha Retroreflective sheeting
EP0693697B1 (en) 1994-07-22 2003-02-19 Nippon Carbide Kogyo Kabushiki Kaisha A method for producing retroreflective sheeting
US5824390A (en) 1994-07-22 1998-10-20 Nippon Carbide Kogyo Kabushiki Kaisha Method for producing retroreflective sheeting using a coupling agent
EP0693697A2 (en) 1994-07-22 1996-01-24 Nippon Carbide Kogyo Kabushiki Kaisha A method for producing retroreflective sheeting
WO1996035970A1 (en) 1995-05-11 1996-11-14 Minnesota Mining And Manufacturing Company Encapsulated lens retroreflective sheeting having thermoplastic polyurethane bonding layer
US5835271A (en) 1995-06-29 1998-11-10 Minnesota Mining And Manufacturing Company Encased retroreflective elements and method for making
WO1997010378A1 (en) 1995-09-15 1997-03-20 Minnesota Mining And Manufacturing Company Retroreflective transfer sheet and applique
US6677030B2 (en) 1996-10-23 2004-01-13 3M Innovative Properties Company Retroreflective articles having tackified acrylic adhesives for adhesion to curved low surface energy substrates
US6156436A (en) 1997-04-04 2000-12-05 3M Innovative Properties Company Use of a crystalline bead bond layer in a retroreflective article
US5959775A (en) 1997-12-23 1999-09-28 3M Innovative Properties Company Urethane/acrylate bead bond for retroreflective articles
US20030006005A1 (en) * 1998-05-29 2003-01-09 3M Innovative Properties Company Prefabricated retroreflective sign
US20030151815A1 (en) 1998-10-30 2003-08-14 Michael Hannington Retroreflective sheeting containing a validation image and methods of making the same
US6677028B1 (en) 1999-09-10 2004-01-13 3M Innovative Properties Company Retroreflective articles having multilayer films and methods of manufacturing same
US6586067B2 (en) 2001-04-02 2003-07-01 Avery Dennison Corporation Encapsulated lens retroreflective sheeting
US20060238871A1 (en) 2005-04-21 2006-10-26 Lee In-Hwan Method of producing a retro-reflective heat transfer film with a transparent protective sheet for whole surface

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
International preliminary report on patentability issued in corresponding International application PCT/US2009/064734 dated Feb. 28, 2011.
International search report and written opinion issued in corresponding International application PCT/US2009/064734 dated Feb. 18, 2010.
Response to International search report and written opinion filed in corresponding International application PCT/US2009/064734 on Jun. 7, 2010.

Also Published As

Publication number Publication date Type
EP2390688A1 (en) 2011-11-30 application
ES2559938T3 (en) 2016-02-16 grant
EP2359168B1 (en) 2016-08-17 grant
US20160297173A1 (en) 2016-10-13 application
US20100124632A1 (en) 2010-05-20 application
US9821531B2 (en) 2017-11-21 grant
CN102282483B (en) 2015-08-05 grant
KR20110087294A (en) 2011-08-02 application
CN102282483A (en) 2011-12-14 application
EP2359168A1 (en) 2011-08-24 application
EP2390688B1 (en) 2016-01-06 grant
ES2600490T3 (en) 2017-02-09 grant
WO2010059600A1 (en) 2010-05-27 application

Similar Documents

Publication Publication Date Title
US3405025A (en) Retro-reflective assembly and method of making the same
US3449158A (en) Method of making a phased lenticular composite strip for optical effects
US3190178A (en) Reflex-reflecting sheeting
US3839129A (en) Reflective foil and process
US5614286A (en) Conformable cube corner retroreflective sheeting
US4897136A (en) Method of making encapsulated-lens retroreflective sheeting
US3005382A (en) Reflex-reflecting sheet materials
US5264063A (en) Method for making flexible retroreflective sheet material
US5691846A (en) Ultra-flexible retroreflective cube corner composite sheetings and methods of manufacture
US4664966A (en) Enclosed-lens retroreflective sheeting having tough, weather-resistant, transparent cover film
US5066098A (en) Cellular encapsulated-lens high whiteness retroreflective sheeting with flexible cover sheet
US5657162A (en) Retroreflective articles with multiple size prisms in multiple locations
US5069964A (en) Flexible, substrate-insular retroreflective sheeting
US3684348A (en) Retroreflective material
US5229882A (en) Colored retroreflective sheeting and method of making same
US5814355A (en) Mold for producing glittering cube-corner retroreflective sheeting
US5840405A (en) Glittering cube-corner retroreflective sheeting
US4648932A (en) High-angularity retroreflective sheeting and method for manufacture
US5780140A (en) Retroreflective microprismatic material with top face curvature and method of making same
US5770124A (en) Method of making glittering cube-corner retroreflective sheeting
US4682852A (en) Reflective sheeting technology
US4505967A (en) High-angularity retroreflective sheeting and method for manufacture
US4075049A (en) Method of preparing retroreflective sheeting
US5171624A (en) Retroreflective microprismatic material and method of making same
US5763049A (en) Formed ultra-flexible retroreflective cube-corner composite sheeting with target optical properties and method for making same

Legal Events

Date Code Title Description
AS Assignment

Owner name: AVERY DENNISON CORPORATION,CALIFORNIA

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:HANNINGTON, MICHAEL E.;REEL/FRAME:023705/0330

Effective date: 20091211

Owner name: AVERY DENNISON CORPORATION, CALIFORNIA

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:HANNINGTON, MICHAEL E.;REEL/FRAME:023705/0330

Effective date: 20091211